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《Acta Chimica Sinica》 1985-09
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ZHAO ZHEN-GUO ZHAO ZHI-JIAN Gu TI-REN~* (Department of Chemistry, Peking University, Beijing)  
The adsorption isotherms of some aromatic compounds (benzoic acid, o-phthalic acid, o-, m-, and p-hydroxy-benzoic acid, phenol and catechol) from water onto activated carbon have been determined at 25℃ and 35℃. Except at very low concentrations, the isotherms can be represented by the Langmuir equation. The standard changes of free energy (⊿G°), enthalpy (⊿H°) and entropy (⊿S°) in adsorption processes have been calculated from the Langmuir parameters. The results so obtained indicate that the value of-⊿H° is less than that of-⊿G°, and ⊿S° is positive. The results also show that generally the entropy term is essential part in ⊿G°. A theory has been proposed to explain positive value of ⊿S°. When dealing with adsorption from solution, the surface of solid must be covered by either the solute or the solvent. Hence, the adsorption of the solute involves two steps: (1) removing the solute from solution and attaching the solute te the surface, (2) removing the solvent from the surface and entering the solvent into the solution. The former step, adsorption of solute, decreases the entropy; and the later step, desorption of solvent, increases the entropy. The entropy change of overall adsorption process is the sum of the entropy changes of two steps. As the molar volume of aromatic compounds studied here are 5~7 times that of water, therefore, the entropy loss on adsorption of solute is less than the entropy gain on desorption of water. This explains why ⊿S° is positive. Along this consideration, it is suggested that ⊿S° may become negative if the molar volume or molar area of solute is similar to or larger than that of solvent. The prediction is supported by the data in literature.
【Fund】: 中国科学院科学基金
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